CA2667905A1 - Photochromic materials demonstrating improved fade rates - Google Patents

Photochromic materials demonstrating improved fade rates Download PDF

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CA2667905A1
CA2667905A1 CA 2667905 CA2667905A CA2667905A1 CA 2667905 A1 CA2667905 A1 CA 2667905A1 CA 2667905 CA2667905 CA 2667905 CA 2667905 A CA2667905 A CA 2667905A CA 2667905 A1 CA2667905 A1 CA 2667905A1
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phenyl
alkoxy
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CA2667905C (en
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Anu Chopra
Patrick M. Brown
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Transitions Optical Inc
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Transitions Optical, Inc.
Anu Chopra
Patrick M. Brown
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/74—Benzo[b]pyrans, hydrogenated in the carbocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/94—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/23—Photochromic filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/145—Heterocyclic containing oxygen as the only heteroatom

Abstract

Various photochromic materials are provided that are essentially free of polymerizable unsaturated groups, and comprise: a) an indeno[2',3':3,4]naphtho[1,2-b]pyran; and b) an electron-withdrawing, non-conjugating group bonded at the 11-position of the indeno[2',3':3,4]naphtho[1,2-b]pyran. Alternative embodiments include various substituents at other positions of the indeno[2',3':3,4]naphtho[1,2-b]pyran. Also provided are photochromic articles including a substrate and one of the above photochromic materials, in contact with at least a portion of the substrate.

Claims (24)

1. A photochromic material that is essentially free of polymerizable unsaturated groups, said photochromic material comprising:
a) an indeno[2',3':3,4]naphtho[1,2-b]pyran;
b) an electron-withdrawing, non-conjugating group bonded at the 11-position of the indeno[2',3':3,4]naphtho[1,2-b]pyran; and c) two groups bonded at the 13-position of the indeno[2',3':3,4]naphtho[1,2-b]pyran, provided that said groups do not combine to form a spirocyclic group.
2. The photochromic material of claim 1 wherein the electron-withdrawing, non-conjugating group comprises an .alpha.-haloalkyl, .alpha.,.alpha.-dihaloalkyl, trihalomethyl group, a perhalo(C2-C10)alkyl group, a perhaloalkoxy group, or the group -O-C(O)-R, wherein R
is a linear or branched group chosen from C1-C10 alkyl, C1-C10 haloalkyl , or perhaloalkyl..
3. The photochromic material of claim 2 wherein the electron-withdrawing, non-conjugating group comprises a trifluoromethyl group.
4. The photochromic material of claim 1 wherein each of the two groups bonded at the 13-position independently comprises a(C1-C6)alkyl group, a(C1-C6)alkoxy group, a hydroxy(C1-C6)alkyl or the polyalkoxylated group T represented by the formula:
-Z[(OC2H4)x (OC3H6)y (OC4H8)z]Z' or -[(OC2H4)x (OC3H6)y (OC4H8)z]Z' wherein -Z is -C(O)- or -CH2- and Z' is hydroxy, epoxy or C1-C3 alkoxy and letters x, y and z are each a number between 0 and 50 and the sum of x, y and z is between 2 and 50.
5. The photochromic material of claim 1 wherein the photochromic material has a closed-form absorption spectrum for electromagnetic radiation that is bathochromically shifted as compared to a closed-form absorption spectrum for electromagnetic radiation of a photochromic material comprising a comparable indeno[2',3':3,4]naphtho[1,2-b]pyran without the electron-withdrawing, non-conjugating group at the 11 -position thereof.
6. A photochromic material that is essentially free of polymerizable unsaturated groups, said photochromic material comprising:
a) an indeno[2',3':3,4]naphtho[1,2-b]pyran;
b) an electron-withdrawing, non-conjugating group bonded at the 11-position of the indeno[2',3':3,4]naphtho[1,2-b]pyran; and c) moderate to strong electron-donating groups bonded at each of the 6- and 7-positions of the indeno[2',3':3,4]naphtho[1,2-b]pyran.
7. The photochromic material of claim 6 wherein the electron-withdrawing, non-conjugating group comprises an a-haloalkyl, a,a-dihaloalkyl, trihalomethyl group, a perhalo(C2-C10)alkyl group, a perhaloalkoxy group, or the group -O-C(O)-R, wherein R
is a linear or branched group chosen from C1-C10 alkyl, C1-C10 haloalkyl , or perhaloalkyl..
8. The photochromic material of claim 7 wherein the electron-withdrawing, non-conjugating group comprises a trifluoromethyl group.
9. The photochromic material of claim 6 wherein each of the two moderate to strong electron-donating groups independently comprises:
(i) the group -OR8', wherein R8' is phenyl(C1-C3)alkyl, C1-C6 alkyl, mono(C1-C6)alkyl substituted phenyl(C1-C3)alkyl, mono(C1-C6)alkoxy substituted phenyl(C1-C3)alkyl, C1-C6 alkoxy(C2-C4)alkyl, C3-C7 cycloalkyl, mono(C1-C4)alkyl substituted C3-C7 cycloalkyl, C1-C6 chloroalkyl, C1-C6 fluoroalkyl, allyl, or R8' is the group, -CH(R9')Q", wherein R9' is hydrogen or C1-C3 alkyl and Q" is -CN, -COOH, -COOCH3, or -COOCH2CH3;
(ii) -N(R15)R16, wherein R15 and R16 each independently comprises hydrogen, C1-C8 alkyl, phenyl, naphthyl, the heteroaromatic groups furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, benzopyridyl and fluorenyl, C1-C8 alkylaryl, cycloalkyl, C4-C20 bicycloalkyl, C5-C20 tricycloalkyl and C1-C20 alkoxyalkyl, wherein said aryl group is phenyl or naphthyl;

(iii) a nitrogen containing ring represented by the following graphic formula:

wherein Y is selected from the group consisting of -CH2-, -CH(R17)-, -C(R17)(R17)-, -CH(aryl)-, -C(aryl)2-, and -C(R17)(aryl)-, and X is selected from the group consisting of -Y-, -O-, -S-, -S(O)-, -S(O2)-, -NH-, -NR17- and -N-aryl, wherein R17 is C1-C6 alkyl, said aryl substituent is phenyl or naphthyl, m is the integer 1, 2 or 3, and p is the integer 0, 1, 2, or 3, provided that when p is 0, X is Y; or (iv) a group represented by one of the following graphic formulae:
wherein R19, R20 and R21 are each hydrogen, C1-C5 alkyl, phenyl or naphthyl, or the groups R19 and R20 may come together to form a ring of 5 to 8 carbon atoms;
and R18 is C1-C6 alkyl, C1-C6 alkoxy, fluoro or chloro.
10. The photochromic material of claim 1 wherein the photochromic material has a closed-form absorption spectrum for electromagnetic radiation that is bathochromically shifted as compared to a closed-form absorption spectrum for electromagnetic radiation of a photochromic material comprising a comparable indeno[2',3':3,4]naphtho[1,2-b]pyran without the electron-withdrawing, non-conjugating group at the 11-position thereof.
11. A photochromic material that is essentially free of polymerizable unsaturated groups, said photochromic material represented by:

wherein:
B and B' are each independently:
a metallocenyl group;
an aryl group that is mono-substituted with a reactive substituent or a compatibilizing substituent;
9-julolidinyl, an unsubstituted, mono-, di- or tri-substituted aryl group chosen from phenyl and naphthyl, an unsubstituted, mono- or di-substituted heteroaromatic group chosen from pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyl, benzopyridyl, indolinyl or fluorenyl, wherein the aryl and heteroaromatic substituents are each independently:
hydroxy, aryl, mono- or di-(C1-C12)alkoxyaryl, mono- or di-(C1-C12)alkylaryl, haloaryl, C3-C7 cycloalkylaryl, C3-C7 cycloalkyl, C3-C7 cycloalkyloxy, C3-C7 cycloalkyloxy(C1-C12)alkyl, C3-C7 cycloalkyloxy(C1-C12)alkoxy, aryl(C1-C12)alkyl, aryl(C1-C12)alkoxy, aryloxy, aryloxy(C1-C12)alkyl, aryloxy(C1-C12)alkoxy, mono- or di-(C1-C12)alkylaryl(C1-C12)alkyl, mono- or di-(C1-C12)alkoxyaryl(C1-C12)alkyl, mono-or di-(C1-C12)alkylaryl(C1-C12)alkoxy, mono- or di-(C1-C12)alkoxyaryl(C1-C12)alkoxy, amino, mono-or di-(C1-C12)alkylamino, diarylamino, piperazino, N-(C1-C12)alkylpiperazino, N-arylpiperazino, aziridino, indolino, piperidino, morpholino, thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidino, C1-C12 alkyl, C1-C12 haloalkyl, C1-C12 alkoxy, mono(C1-C12)alkoxy(C1-C12)alkyl, , halogen or -C(=O)R22, wherein R22 is -OR23, -N(R24)R25, piperidino or morpholino, wherein R23 is allyl, C1-C6 alkyl, phenyl, mono(C1-C6)alkyl substituted phenyl, mono(C1-C6)alkoxy substituted phenyl, phenyl(C1-C3)alkyl, mono(C1-C6)alkyl substituted phenyl(C1-C3)alkyl, mono(C1-C6)alkoxy substituted phenyl(C1-C3)alkyl, C1-C6 alkoxy(C2-C4)alkyl or C1-C6 haloalkyl, and R24 and R25 are each independently C1-C6 alkyl, C5-C7 cycloalkyl or a substituted or an unsubstituted phenyl, wherein said phenyl substituents are each independently alkyl or C1-C6 alkoxy;
an unsubstituted or mono-substituted group chosen from pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolidino, phenothiazinyl, phenoxazinyl, phenazinyl and acridinyl, said wherein said substituents are each independently C1-C12 alkyl, alkoxy, phenyl or halogen;
a 4-substituted phenyl, the substituent being a dicarboxylic acid residue or derivative thereof, a diamine residue or derivative thereof, an amino alcohol residue or derivative thereof, a polyol residue or derivative thereof, -(CH2)-, -(CH2)e or -[O-(CH2)e]f-, wherein e is an integer ranging from 2 to 6 and f is an integer ranging from 1 to 50, and wherein the substituent is connected to an aryl group of another photochromic material;
a group represented by:

wherein P is -CH2- or -O-; Q''' is -O- or substituted nitrogen, the substituted nitrogen substituents being hydrogen, C1-C12 alkyl or C1-C12 acyl, provided that when Q''' is substituted nitrogen, P is -CH2-; each R26 is independently C1-C12 alkyl, C1-C12 alkoxy, hydroxy or halogen; R27 and R28 are each independently hydrogen or C1-alkyl; and j is an integer ranging from 0 to 2; or B and B' taken together form a fluoren-9-ylidene or mono- or di-substituted fluoren-9-ylidene, wherein said fluoren-9-ylidene substituents are each independently C1-C12 alkyl, C1-C12 alkoxy or halogen;
R5, R8, R9 and R12 each independently comprises:
hydrogen, C1-C6 alkyl, chloro, fluoro, bromo, C3-C7 cycloalkyl or a unsubstituted, mono- or di-substituted phenyl, wherein said phenyl substituents are each independently C1-C6 alkyl or C1-C6 alkoxy;
-OR40 or -OC(=O)R40, wherein R40 is hydrogen, amine, alkylene glycol, polyalkylene glycol, C1-C6 alkyl, phenyl(C1-C3)alkyl, mono(C1-C6)alkyl substituted phenyl(C1-C3)alkyl, mono(C1-C6)alkoxy substituted phenyl(C1-C3)alkyl, (C1-C6)alkoxy(C2-C4)alkyl, C3-C7 cycloalkyl, mono(C1-C4)alkyl substituted C3-C7 cycloalkyl or an unsubstituted, mono- or di-substituted phenyl, wherein said phenyl substituents are each independently C1-C6 alkyl or C1-C6 alkoxy;

a reactive substituent or a compatibilizing substituent;
a 4-substituted phenyl, the substituent being a dicarboxylic acid residue or derivative thereof, a diamine residue or derivative thereof, an amino alcohol residue or derivative thereof, a polyol residue or derivative thereof, -(CH2)-, -(CH2)e-or -[O-(CH2)e]f-, wherein e is an integer ranging from 2 to 6, and f is an integer ranging from 1 to 50, and wherein the substituent is connected to an aryl group of another photochromic material;
-N(R41)R42, wherein R41 and R42 are each independently hydrogen, C1-C8 alkyl, phenyl, naphthyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, benzopyridyl, fluorenyl, C1-C8 alkylaryl, C3-C8 cycloalkyl, C4-C16 bicycloalkyl, C5-C20 tricycloalkyl or C1-C20 alkoxy(C1-C6)alkyl, or R41 and R42 come together with the nitrogen atom to form a C3-C20 hetero-bicycloalkyl ring or a C4-C20 hetero-tricycloalkyl ring;
a nitrogen containing ring represented by:
wherein each -V- is independently chosen for each occurrence from -CH2-, -CH(R43)-, -C(R43)2-, -CH(aryl)-, -C(aryl)2- and -C(R43)(aryl)-, wherein each R43 is independently C1-C6 alkyl and each aryl is independently phenyl or naphthyl; -W- is -V-, -O-, -S-, -S(O)-, -SO2-, -NH-, -N(R43)- or -N(aryl)-; s is an integer ranging from 1 to 3;
and r is an integer ranging from 0 to 3, provided that if r is 0, then -W- is the same as -V;
or a group represented by:

wherein each R44 is independently C1-C6 alkyl, C1-C6 alkoxy, fluoro or chloro;
R45, R46 and R47 are each independently hydrogen, C1-C6 alkyl, phenyl or naphthyl, or R45 and R46 together form a ring of 5 to 8 carbon atoms, and p is an integer ranging from 0 to 3;
R6 and R7 each independently comprises a moderate to strong electron-donating group;

R10 comprises any of the groups discussed above with respect to R5, R8, R9 and R12 or a metallocenyl group;
R11 comprises an electron-withdrawing, non-conjugating group;
R13 and R14 do not form a spirocyclic group and each independently comprises an alkyl group or an alkoxy group.
12. The photochromic material of claim 11 wherein each of R6 and R7 independently comprises:
(i) the group -OR8', wherein R8' is phenyl(C1-C3)alkyl, C1-C6 alkyl, mono(C1-C6)alkyl substituted phenyl(C1-C3)alkyl, mono(C1-C6)alkoxy substituted phenyl(C1-C3)alkyl, C1-C6 alkoxy(C2-C4)alkyl, C3-C7 cycloalkyl, mono(C1-C4)alkyl substituted C3-C7 cycloalkyl, C1-C6 chloroalkyl, C1-C6 fluoroalkyl, allyl, or R8' is the group, -CH(R9')Q", wherein R9' is hydrogen or C1-C3 alkyl and Q" is -CN, -COOH, -COOCH3, or -COOCH2CH3;
(ii) -N(R15)R16, wherein R15 and R16 each independently comprises hydrogen, C1-C8 alkyl, phenyl, naphthyl, the heteroaromatic groups furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, benzopyridyl and fluorenyl, C1-C8 alkylaryl, C20 cycloalkyl, C4-C20 bicycloalkyl, C5-C20 tricycloalkyl and C1-C20 alkoxyalkyl, wherein said aryl group is phenyl or naphthyl;
(iii) a nitrogen containing ring represented by the following graphic formula:

wherein Y is selected from the group consisting of -CH2-, -CH(R17)-, -C(R17)(R17)-, -CH(aryl)-, -C(aryl)2-, and -C(R17)(aryl)-, and X is selected from the group consisting of -Y-, -O-, -S-, -S(O)-, -S(O2)-, -NH-, -NR17- and -N-aryl, wherein R17 is C1-C6 alkyl, said aryl substituent is phenyl or naphthyl, m is the integer 1, 2 or 3, and p is the integer 0, 1, 2, or 3, provided that when p is 0, X is Y; or (iv) a group represented by one of the following graphic formulae:

wherein R19, R20 and R21 are each hydrogen, C1-C5 alkyl, phenyl or naphthyl, or the groups R19 and R20 may come together to form a ring of 5 to 8 carbon atoms;
and R18 is C1-C6 alkyl, C1-C6 alkoxy, fluoro or chloro.
13. The photochromic material of claim 11 wherein R11 comprises an a-haloalkyl, .alpha.,.alpha.-dihaloalkyl, trihalomethyl group, a perhalo(C2-C10)alkyl group, a perhaloalkoxy group, or the group -O-C(O)-R, wherein R is a linear or branched group chosen from C1-C10 alkyl, C1-C10 haloalkyl , or C1-C10 perhaloalkyl..
14. A photochromic material chosen from:
a) 3,3-di(4-methoxyphenyl)-6,7-dimethoxy-11-trifluoromethyl-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran;
b) 3,3-di(4-methoxyphenyl)-6-methoxy-7-morpholino-11-trifluoromethyl-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran;
c) 3-(4-methoxyphenyl)-3-(4-(2-hydroxyethoxy)phenyl)-6,7-dimethoxy-11-trifluoromethyl-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran;
d) 3-(4-methoxyphenyl)-3-(4-(2-hydroxyethoxy)phenyl)-6-methoxy-7-morpholino-11-trifluoromethyl-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran;
e) 3-(4-methoxyphenyl)-3-(4-fluorophenyl)-6,7-dimethoxy-11-trifluoromethyl-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran;
f) 3-(4-morpholinophenyl)-3-(4-fluorophenyl)-6,7-dimethoxy-11-trifluoromethyl-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran;
g) 3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-6,7-dimethoxy-11-trifluoromethyl-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran;
h) 3-(4-methoxyphenyl)-3-(4-butoxyphenyl)-6,7-dimethoxy-11-trifluoromethyl-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran;
i) 3,3-di-(4-(2-methoxyethoxy)phenyl)-6,7-dimethoxy-11-trifluoromethyl-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran;

j) 3-(4-methoxyphenyl)-3-(4-ethoxyphenyl)-6,7-dimethoxy-11-trifluoromethyl-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran;
k) 3-(4-methoxyphenyl)-3-(4-butoxyphenyl)-6-methoxy-7-morpholino-11-trifluoromethyl-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran;
l) 3,3-di-(4-fluorophenyl)-6-methoxy-7-morpholino-11-trifluoromethyl-13-butyl-13-(2-(2-hydroxyethoxy)ethoxy)-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; and m) mixtures thereof.
15. A photochromic article comprising:
(a) a substrate; and (b) a photochromic material in contact with at least a portion of the substrate, wherein the photochromic material is essentially free of polymerizable unsaturated groups and comprises:
i) an indeno[2',3':3,4]naphtho[1,2-b]pyran;
ii) an electron-withdrawing, non-conjugating group bonded at the 11-position of the indeno[2',3':3,4]naphtho[1,2-b]pyran; and iii) two groups bonded at the 13-position of the indeno[2',3':3,4]naphtho[1,2-b]pyran provided that said groups do not combine to form a spirocyclic group.
16. The photochromic article of claim 15 wherein the electron-withdrawing, non-conjugating group comprises an .alpha.-haloalkyl,.alpha.,.alpha.-dihaloalkyl, trihalomethyl group, a perhalo(C2-C10)alkyl group, a perhaloalkoxy group, or the group -O-C(O)-R, wherein R
is a linear or branched group chosen from C1-C10 alkyl, C1-C10 haloalkyl , or perhaloalkyl..
17. The photochromic article of claim 16 wherein the electron-withdrawing, non-conjugating group comprises a trifluoromethyl group.
18. The photochromic article of claim 15 wherein each of the two groups bonded at the 13-position independently comprises an alkyl group or an alkoxy group.
19. A photochromic article comprising:
(a) a substrate; and (b) a photochromic material in contact with at least a portion of the substrate, wherein the photochromic material is essentially free of polymerizable unsaturated groups and comprises:
i) an indeno[2',3':3,4]naphtho[1,2-b]pyran;
ii) an electron-withdrawing, non-conjugating group bonded at the 11-position of the indeno[2',3':3,4]naphtho[1,2-b]pyran; and iii) moderate to strong electron-donating groups bonded at each of the 6- and 7-positions of the indeno[2',3':3,4]naphtho[1,2-b]pyran.
20. The photochromic article of claim 19 wherein the electron-withdrawing, non-conjugating group comprises an .alpha.-haloalkyl, .alpha.,.alpha.-dihaloalkyl, trihalomethyl group, a perhalo(C2-C10)alkyl group, a perhaloalkoxy group, or the group -O-C(O)-R, wherein R
is a linear or branched group chosen from C1-C10 alkyl, C1-C10 haloalkyl , or perhaloalkyl..
21. The photochromic article of claim 20 wherein the electron-withdrawing, non-conjugating group comprises a trifluoromethyl group.
22. The photochromic article of claim 19 wherein each of the two moderate to strong electron-donating groups independently comprises:
(i) the group -OR8', wherein R8' is phenyl(C1-C3)alkyl, C1-C6 alkyl, mono(C1-C6)alkyl substituted phenyl(C1-C3)alkyl, mono(C1-C6)alkoxy substituted phenyl(C1-C3)alkyl, C1-C6 alkoxy(C2-C4)alkyl, C3-C7 cycloalkyl, mono(C1-C4)alkyl substituted C3-C7 cycloalkyl, C1-C6 chloroalkyl, C1-C6 fluoroalkyl, allyl, or R8' is the group, -CH(R9')Q", wherein R9' is hydrogen or C1-C3 alkyl and Q" is -CN, -COOH, -COOCH3, or -COOCH2CH3;
(ii) -N(R15)R16, wherein R15 and R16 each independently comprises hydrogen, C1-C8 alkyl, phenyl, naphthyl, the heteroaromatic groups furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, benzopyridyl and fluorenyl, C1-C8 alkylaryl, C20 cycloalkyl, C4-C20 bicycloalkyl, C5-C20 tricycloalkyl and C1-C20 alkoxyalkyl, wherein said aryl group is phenyl or naphthyl;
(iii) a nitrogen containing ring represented by the following graphic formula:

wherein Y is selected from the group consisting of -CH2-, -CH(R17)-, -C(R17)(R17)-, -CH(aryl)-, -C(aryl)2-, and -C(R17)(aryl)-, and X is selected from the group consisting of -Y-, -O-, -S-, -S(O)-, -S(O2)-, -NH-, -NR17- and -N-aryl, wherein R17 is C1-C6 alkyl, said aryl substituent is phenyl or naphthyl, m is the integer 1, 2 or 3, and p is the integer 0, 1, 2, or 3, provided that when p is 0, X is Y; or (iv) a group represented by one of the following graphic formulae:
wherein R19, R20 and R21 are each hydrogen, C1-C5 alkyl, phenyl or naphthyl, or the groups R19 and R20 may come together to form a ring of 5 to 8 carbon atoms;
and R18 is C1-C6 alkyl, C1-C6 alkoxy, fluoro or chloro.
23. The photochromic article of claim 19 wherein the photochromic article is an optical element, said optical element being at least one of an ophthalmic element, a display element, a window, a mirror, and a liquid crystal cell element.
24. The photochromic article of claim 23 wherein the optical element is an ophthalmic element, said ophthalmic element being at least one of a corrective lens, a non-corrective lens, a magnifying lens, a protective lens, a visor, goggles and a lens for an optical instrument.
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